Processes for thermally reacting hydrocarbons



June 11, F E FREY ET AL 2,401,922

PROCESS FOR THERMALLY REACTING HYDROCARBONS Original Filed Jan. 51, 1936 Pro/2107*? dye/17* /2 E1 9 1 "i a Hydrocarbon f/liid Pramofed 7'her'ma/ 3 Eeacf/on From 0 fed 777erma/ fieac f/bn Reacf/bn Producf f0 Se oaraf/fly alien/7S FREDERICK E y HAROLD I HEPP GLEN H. MOREY BY 7 MM, M "W AT ORNE INVENTOR Patented June 11, 1946 PROCESSES FOR THERMALLY REACTING HYDROCARBON S Frederick E. Frey and Harold J. Hem Bartlesville, kla., and Glen H. Morey, Terre Haute, Ind., assignors to Phillips Petroleum Company, a corporation of Delaware Original application January 31, 1936, Serial No. 61,814. Divided and this application April 2,

1941, Serial No. 386,430

3 Claims.

This invention relates to processes for thermally reacting hydrocarbons and more specifically to means for more efiiciently carrying out such reactions with the aid of reaction promoting agents whereby lower temperatures and shorter reaction periods may be employed than those required for the ordinary uncatalyzed reaction. This application is a division of our copending application Serial No. 61,814, filed January 31, 1936, now U. S. Patent 2,259,630, issued October 21, 1941.

Thermal reaction or cracking is commonly applied to hydrocarbon oils to produce hydrocarbons of lower molecular weight such as gasoline and gas, and to normally gaseous hydrocarbons to produce normally gaseous olefins and parafiins through scission reactions and also hydrocarbons of higher molecular weight through polymerization. The proportion of such higher hydrocarbons may be small when cracking is conducted at low pressures but may be formed in large amount when high pressures are employed. Volatile normally liquid hydrocarbons produced in this way are used as motor fuel, and normally gaseous olefin hydrocarbons obtained by cracking in turn may be converted into motor fuel by polymerization or put to a variety of other uses.

Pyrolytic reactions of saturated and unsaturated hydrocarbons may be induced under conditions of temperature and time too mild to bring about ordinary homogeneous reaction by means of catalytic materials which are not destroyed in the process. The course of the reaction is dependent on the catalytic material used. Thus dehydrogenation catalysts will effect dehydrogenation of saturated hydrocarbons. Other catalytic materials effect scission reactions together with more or less dehydrogenation, while still other catalysts are applicable to the conversion of unsaturated hydrocarbons to yield products of higher molecular weight.

Our invention provides a new and different method of bringing about thermal decomposition reactions under milder conditions than those required for the ordinary uncatalyzed reactions, which is based upon the discovery that such thermal decomposition reactions can be induced by other reactions occurring concomitantly. We have discovered that certain organic compounds, themselves decomposed readily by heat will in the presence of saturated and unsaturated hydrocarbons induce thermal reaction in the latter under conditions of heating too mild to effect reaction ordinarily, the organic compound present being decomposed in the process. We have found that such a compound, which may be designated a reaction promoting agent, will induce the decomposition of ten and more molecular equivalents of hydrocarbon under approprite conditions which are a part of this invention.

This invention ha for its objects the use of such compounds to effect thermal reaction of saturated and also unsaturated hydrocarbons of reaction vessels are exposed. Another object is the control of the thermal conversion operation by the controlled introduction of a reaction promoting agent. Other objects will be apparent as the description proceeds.

We have found that class of the metal alkyls which will volatilize without decomposition to show reaction promoting action in high degree. Zinc, cadmium, mercury, and lead alkyls are particularly suitable, all of which decompose quite rapidly below 400" C. The nature of the alkyl groups may vary widely. .I'he methyl and ethyl metal alkyls are usually preferable since they are somewhat more stable to heat than the higher homologs and are yet sufficiently readily decomposed to exert strong reaction promoting action upon hydrocarbons. Alkylene oxides such as ethylene oxide likewise show high promoting activity. A more mild promoting action is exhibited by hydrocarbons which may nevertheless be advantageously utilized since the latter are comparatively inexpensive. The decomposition temperature of the hydrocarbon added aspromoter should be lower than that of the hydrocarbons the decomposition of which is to be promoted. In general these promoting agents are organic compounds having a decomposition temperature lower than that of the hydrocarbons in which thermal reaction is to be induced. The mechanism of the promoting action is obscure, but appears to be attributable to breaking of the metal to carbon bond of a metal alkyl of an oxygen to carbon bond of an alkylene oxide or in the case of hydrocarbons, of a carbon to carbon bond to yield active molecules containing unsatisfied valences which induce a chain reaction wherein activation is transferred from molecule to molecule of hydrocarbon accompanied by a series of resultant molecular reactions. Several reactions which proceed 'by a chain mechanism are known, which take place with evolution of heat and the initiating of such reaction by various means has been described. The thermal reactions of the parafiins usually absorb heat,

' the simple thermal decomposition absorbs heat strongly. However, the chain mechanism will account for the induced decomposition of many equivalents of paraflin by the promoting agents described, if it be assumed that chain reactions are possible of an endothermic type wherein heat is not developedby reaction which may sustain reaction through the formation of thermally hot molecules but which must do so through structural activation.

The paraifins other than methane and cycloparafiins are susceptible to promoted decomposition and reaction with the agents described, as are also the unsaturated hydrocarbons to yield products of both lower and higher molecular weight. The promoting agents may comprise many difierent molecular species, and promoting action is not limited to the classes of compounds described. The presence of the alkylene oxygen grouping in the molecule and carbon to metal linkages is responsible for the strong promoting action observed with metal alkyl and alkylene oxides. In the case of hydrocarbons as promoting agents, the hydrocarbon introduced as promoting agent should be more readily .pyrolyzed than the hydrocarbons whose reaction is to be promoted. The comparative thermal stabilities. of many hydrocarbons are known and in general stability decreases as the homologous series is ascended.

Ethane and propane are among the more thermally stable hydrocarbons and predominantly saturated hydrocarbons of higher molecular weight'are very suitable as promoting agents to induce thermal reactions. The adjacent homologs of higher molecular weight, propane and butane respectively, exert a substantial degree of promoting action, and higher paraifins are somewhat more efiicient, such as hydrocarbon distillate boiling in the gasoline range or somewhat above. A substantial .quantity of promoting agent greater than 2 per cent of the hydrocarbon to be thermally reactedwill usually be required,

and when the concomitant decomposition of the promoting hydrocarbon yieldsdesirable products, large proportions may be used advantageously. The thermal reaction promoted as described may be one which is conducted at low pressure to produce hydrocarbons of lower molecular weight, or

to thermally convert normally gaseous or higher hydrocarbons. Olefins may be present and take part in the reaction. Under high pressures products of higher molecular weight than the hydro-- carbons. treated result, and thermal reaction through conduit 2;

it may be one conducted at high pressure either promoting agents and can be readily determined by experiment.

Figure 1 illustrates diagrammatically one embodiment of the present invention; and, one em bodiment of the process may be practiced as is shown in Figure 1. Hydrocarbon fluid such as a petroleum distillate enters through conduit I and mingles with the promoting agent entering The mixture passes through a heating element 3 wherein it is heated to a temperature and for a time sufficient to effect thermal reaction and largely destroy the reaction promoting agent, whereby the petroleum distillate is thermally reacted and then discharged through conduit 4.

When the decomposition temperature of the promoting agent'is particularly low or the temperature of uncatalyzed decomposition of the hydrocarbon fluid is particularly high, a decreased consumption of promoting agent results from the heating of the hydrocarbon to reaction temperature level and adding promoting agent during the period of the reaction and subsequent to the ing through conduit 2a is divided into a plurality of streams in conduits 5, 6 and 1 through which it passes to coil 3a and is dispersed in the hydrocarbon stream. The thermally reacted hydrocarbon is discharged through conduit 4a. The inlets 5, 6 and 1 are suitably so spaced and so great in number that destruction of the promoting agent is not wholly completed in the hydrocarbon stream between successive additions of the promoting agent. hydrocarbons are then discharged from heating coil 3a through conduit 4a.

Example 1.--A stream of n-butaneunder a pressure slightly below atmospheric was passed through a heated glass tube wherein it was maintained at 500 C. for 7 seconds. Into the butane was introduced 2 mol. per cent of mercurydimethyl vapor as it entered the heated tube. The gas issuing from the tube was found to have the following composition (volume per cent). I

The mercury dimethyl was found to have virtually completely decomposed. About 6 molecules of butane were decomposed per molecule of mercury dimethyl introduced In an identical experiment, except that mercury dimethyl was not introduced, decomposition of less than 1 per cent of the butane took place. By increasing the temperature to 575 C. and the reaction time to 25 seconds an equivalent extent of decomposition was brought about in the absence of the alkyl. The composition of the products was virtually the same except for a slightly lower methane content, the discrepancy being The thermally reacted about equivalent to the methane which the mercury dimethyl destroyed may have contributed.

Example 2.-In an experiment similar to that of Example 1, n-butane was heated to 555 C.

Having described our invention, what we claim is:

1. A process for the pyrolytic reaction of nor- .mally gaseous hydrocarbons of higher molecular with portionwise addition of mercury dimethyl 5 weight than methane to form higher boiling to the reaction zone at intervals representing hydrocarbons by scission and polymerization. 0.35 second of reaction time, during-which time which comprises maintaining such normally gasperiod about 70 per cent of themercury dimethyl eous hydrocarbons under a high pressure and at present was destroyed between consecutive addiconditions of temperature and time such that tions. Anincreased efiiciency in the reaction prounpromoted pyrolytic reaction to form higher moting effect was obtained, 18.3 molecules of boiling hydrocarbons is undesirably limited and butane being decomposed per molecule of mercury adding to said hydrocarbons between two and dimethyl consumed, while introduction of all the ten mol per cent of an alkylene oxide, which can mercury dimethyl at one point yielded at 557 C. be volatilized without decomposition, to promote only 6.5 molecules butane decomposed per molesaid pyrolytic reaction of said hydrocarbons to cule of the alkyl. form higher boiling hydrocarbons.

Example 3.In an experiment of the type of 2. A process for the pyrolytic reaction of nor- Example 1, n-butane was heated to 561 C. for a mally gaseous paraflin hydrocarbons of higher time of 1.7 seconds, too brief to effect ordinary molecular weight than methane to form higher decomposition of the butane. One and sevenboiling hydrocarbons by scission and polymerizatenths mol per cent of ethylene oxide, introduced tion, which comprises maintaining such norwith the butane at the reaction tube inlet brought mally gaseous hydrocarbons under a high presabout 9.0 mol per cent decomposition of the sure and at conditions of temperature and time butane. such that unpromoted pyrolytic reaction to form Example 4.--n-Butane was passed at atmoshigher boiling. hydrocarbons is undesirably limited pheric pressure through a heated glass tube in and adding to said paraffin hydrocarbons between admixture with varying amounts of n-decane, two and ten mol per cent of an'alkylene oxide, and the extent of decomposition determined. which can be volatilized without decomposition, Undecomposed decane was determined as well as to promote said pyrolytlo reaction of said paraffin olefin content of the thermally treated material. hydrocarbons to form higher boiling hydrocar- After deducting the olefins contributed by the bons. I decane decomposed, the remainder, which re- 3. A process for the pyrolytic reaction of norsulted from butane decomposition, served as an mally gaseous paraflin hydrocarbons of higher index of extent of butane decomposition, butane molecular weight than methane to form higher decomposition producing 91 volumes of olefin per boiling hydrocarbons by scission and polymeriza- 100 volume of butane decomposed. tion, which comprises maintaining such a paraffin The following tabulation shows the accelerahydrocarbon under a high pressure at conditions tion in the decomposition of butane induced by of temperature and time such that unpromoted the decomposition of the decane present. pyrolytic reaction to form higher boilinghydro- Mol per Total Oleflns Olefins Fraction cent Per cent Butane olefins formed formed Per cent of butane (k) (Corr. Temperature, C. decanein ofdecane (08 gas) formed from from of butane cracked to 575 samples cracked (cm gas) decane butane cracked per sec. 0.)

cracked (cc. gas; (cc. gas) (k) as 30 163 10.0 4.0 15.9 10.8 0.0004 0.0100 2.4 so 194 19.9 3.2 10.7 9.0 0.0082 0. 0095 0.0 275 18.8 18.8 7.0 0.0002 0.0002

In similar experiments with the more diflicultly carbons is undesirably limited, and admixing decomposed ethane and propane a similar acwith said paraflin hydrocarbon a plurality of celerating effect was observed on the addition of times during said period of reaction not more butane, pentanes, and neopentane. than ten mol per cent of ethylene oxide to pro- From the foregoing it is believed that the procmote pyrolytic reaction of said paraflin hydroess may be readily understood by those skilled in carbon to form higher boiling hydrocarbons. the art and it is manifest that changes may be made in the details as set forth without departing FREDERICK E. FREY. from the spirit of the invention as expressed in 5 HAROLD J. HEPP.

the following claims.

GLEN H. MOREY. 

